Perfluoroalkylalkylmonocarboxylic acid esters

ABSTRACT

PERFLUOROALKYLALKYLMONOCARBOXYLIC ACID ESTERS ARE PROVIDED WHICH ARE DERIVED FROM PERFLUORO-ACIDS AND ALIPHATIC EPOXIDES. THESE ESTERS CONTAIN AT LEAST ONE PERFLUOROALKYL RADICAL WITH 4 TO 14 CARBON ATOMS, WHICH IS BONDED OVER AN ALKYLENE BRIDGE WITH 1 TO 10 CARBON ATOMS TO THE CARBOXYL GROUP, WHICH CARBOXYL GROUP IS ESTERIFIED WITH AN EPOXIDE CONTAINING FURTHER CONDENSABLE GROUPS IN THE TERMINAL POSITION SUCH AS HALOGEN ATOMS OR A HYDROXYL GROUP. THE PERFLUOROALKYLALKYLMONOCARBOXYLIC ACID ESTERS ARE USED FOR TREATING POROUS OR NON POROUS SUBSTRATES, PERFERABLY FOR THE PRODUCTION OF OLEOPHOBIC FURNISHES ABOVE ALL ON FIBROUS MATERIALS SUCH AS TEXTILES AND PAPERS.

tj i d States Patent 011516 Int. 01. con 39/62,- D06m 15/48 US. Cl.260-408 10 Claims ABSTRACT OF THE DISCLOSUREPerfiuoroalkylalkylmonocarboxylic acid esters are provided which arederived from perfluoro-acids and aliphatic epoxides. These esterscontain at least one perfluoroalkyl radical with 4 to 14 carbon atoms,which is bonded over an alkylene bridge with 1 to 10 carbon atoms to thecarboxyl group, which carboxyl group is esterified with an epoxidecontaining further condensable groups in the terminal position such ashalogen atoms or a hydroxyl group.

The perfluoroalkylalkylmonocarboxylic acid esters are used for treatingporous or non porous substrates, preferably for the production ofoleophobic furnishes above all on fibrous materials such as textiles andpapers.

The subject of the present application areperfiuoroalkylalkylmonocarboxylic acid esters which contain (a) at leastone perfluoroalkyl radical with 4 to 14 carbon atoms, which is bondedvia an alkylene group with 1 to 10 carbon atoms to a carboxyl group,which is bonded in an esterlike manner to (b) an acyclic, aliphaticradical which is substituted by a hydroxyl group in the 2-position tothe ester bridge, the radical containing yet further condensable groupsin the terminal position.

The alkylene group via which the perfiuoroalkyl radical is bonded to thecarboxyl group, can be acyclic-branched or unbranched-or cyclic. Theacyclic radicals contain 1 to 10 carbon atoms, whilst the cycloalkyleneradicals possess or 6 ring carbon atoms. The ethylene, n-butylene,n-decylene, isopropylene, or cyclohexylene radical may be mentioned asexamples.

Preferred compounds are perfiuoroalkylalkylmonocarboxylic acid esters ofthe formula 1 n-o-ooo-a-x wherein R denotes a penfiuoroalkyl radicalwith 4 to 14 carbon atoms, Q denotes an acyclic alkylene radical with 1to carbon atoms, preferably a n-alkylene radical, or a cycloalkyleneradical with 5 or 6 ring carbon atoms, A denotes an alkyl radical whichis optionally substituted further and X denotes a halogen atom, ahydroxyl group or a Y-O-(CH CH O),, group, wherein Y represents ahydrogen atom, an alkyl radical or an epoxyalkyl radical, n is aninteger from 1 to 20, and the hydroxyl group (1) is in the 2-position tothe R-COO- group.

Amongst these, per-fluoroalkylalkylmonocarboxylic acid esters of theformula 3,819,668 Patented June 25, 1974 wherein R, A and X have theindicated meaning, p denotes an integer from 1 to 10, preferably 2 to 6,and the hydroxyl group (1) is in the 2-position to the group, are ofparticular interest.

Amongst these compounds, those of the formula [Ho-1 )HAzX 1 wherein R, Xand p have the indicated meaning, A de notes a hydrogen atom or an alkylradical and A denotes an alkylene radical, are particularly suitable.

A preferred position is occupied here by theperfluoroalkylalkylmonocarboxylic acid esters of the formula wherein Rhas the indicated meaning, A, denotes a hydrogen atom or an alkylradical with 1 to 8 carbon atoms, A, denotes an alkylene radical with 1to 8 carbon atoms and X denotes a chlorine atom, a bromine atom,hydroxyl group or Y --O(CH CH 0),,- group, wherein Y rep resents ahydrogen atom or an alkyl with 1 to 4 carbon atoms or epoxyalkyl groupwith 2 to 4 carbon atoms, and n is an integer from 1 to 20, and p is aninteger from 2 to 6.

Compounds of particular practical interest are those of the formulawherein R, p and A, have the indicated meaning, A denotes a hydrogenatom, a methyl group or an ethyl group, and X denotes a chlorine orbromine atom or a hydroxyl or Y -O(CH CH O) group, wherein Y denoteshydrogen, methyl or glycidyl and n denotes an integer from 1 to 15.

Amongst these, the perfluoroalkylalkylmonocarboxylic acid esters whichcorrespond to the formula wherein R and p have the indicated meaning andX is chlorine or preferably hydroxyl, are of importance.

The perfluoroalkyl radical of the perfiuoroalkylalkylmonocarboxylic acidesters according to the invention preferably contains 5 to 11, orespecially 7 to 9, carbon atoms. The perfluoroalkyl radical can beeither branched or unbranched, that is to say it is also possible foriso-perfluoroalkyl radicals, for example of the formula wherein mrepresents an integer having a value of 1 to 11,

to be present. However, n-perfiuoroalkyl radicals are always preferred.Further, the perfluoroalkyl radical can also be a w-H-perfiuoroalkylradical.

3 As examples, there may be mentioned theperfluoroalkylalkylmonocarboxylic acid esters of the formula Theperfluoroalkylmonocarboxylic acid esters according to the invention areobtained by reaction (1) of a perfluoroalkylalkylmonocarboxylic acid,which contains a perfluoroalkyl radical with 4 to 14 carbon atoms, whichis bonded via an alkylene bridge with 1 to 10 carbon atoms to thecarboxyl group, with (2) an acyclic, aliphatic epoxide which containsyet further condensable groups in the terminal position. The reactiontemperature is between 20 and 70 0., preferably between 20 and 40 C.Depending on the reaction temperature and the reactivity of thereactants, the reaction takes 1 to 24 hours, but is in general completeafter 4 to 8 hours. Preferably, the reaction is allowed to take place inthe presence of a catalyst, such as for example anhydrous sodiumacetate. The reaction is appropriately carried out in a solvent, such asfor example ethyl acetate.

The new perfluoroalkylalkylmonocarboxylic acid esters of the formula (I)or (II) are manufactured by reaction of a perfiuoro-acid of the formulax R-Q-COOH (X I) R-(CHz)pCOOH as component (1) with an epoxide of theformula (XII) O AX as component (2) wherein R, Q, P, A and X have theindicated meaning.

The compounds of the formula (III) are manufactured analogously,employing, as component (2) an epoxide of the formula (XIII) CH-Ar HAz-Xwherein A A and X have the indicated meaning.

To manufacture the compounds of the formulae (VI) or (V), epoxides ofthe formulae wherein A A A X and X have the indicated meaning, are used.

Compounds of the formula (VI) are obtained by using epichlorohydrin orglycidol as component (2).

The following examples of hydroxyalkylepoxides which can be easilyprepared and can subsequently easily be esterified may further bementioned, without thereby restricting the epoxides amenable to thereaction according to the invention with respect to their number and thenature of their condensable grouping: 9-epoxyoctadecanol- 1,1-epoxy-octanol-3, 1-epoxy-nonanol-4, 1-epoxy-4- methy1hexanol-4,2-epoxy-5-methylheptanol-5, l-epoxy-S- methylpentanol-4,4-epoxypentanol-1, 3-epoxypentanol-1 and 1-epoxypentanol-4.

The preparation of the particularly interestingperfluoroalkylalkylmonocarboxylic acid esters of which theperfiuoroalkyl radical contains 5 to 11, preferably 7 to 9, carbon atomsis achieved by reacting a perfiuoroalkylmonocarboxylic acid with 5 to11, preferably 7 to 9, car- 4 bon atoms in the perfluoroalkyl radical,with the component (2). In the formula (XI), p is preferably a numberfrom 2 to 6, especially 2, 4 or 6.

The reaction of a perfluoroalkylalkylmonocarboxylic acid with an epoxidenecessarily yields an isomer mixture of twoperfluoroalkylalkylmonocarboxylic acid hydroxyalkyl esters, since thecarboxyl group and hydroxyl group can add to either carbon atom of theepoxide grouping. This formation of an isomer mixture is expressed inthe formulae (III) to (V1), (WI) and (IX), in that the particularpositions of the substituents are not fixed therein.

The reaction of 2,2,3,3-H-pentadecafluorodecylic acid withepichlorohydrin, which may be mentioned as an example, yields thefollowing isomer mixture:

CF (CF) -CHzCHz-COOH cHz cHoHzcl (XVII) 01 ,(0Feb-CHzCHz-COO-CHz-CH-CHgCl and (XVIIIa) (XVIIIb) c F;,(O Fz)6CH2CH2-C 0O-CH-CHQCI HgOH As a result of the presence of free hydroxyl groups, theperfluoroalkylalkylmonocarboxylic acid esters according to the inventionreact with compounds which contain several functional groups capable ofreacting with hydroxyl groups, such as 1,2-epoxide groups, isocyanategroups, acrylic groups, methylol groups, methylol groups etherified withlower alcohols, aldehyde groups, easily hydrolysable ester groups andthe like. Such polyfunctional compounds are therefore suitable for useas crosslinking components or curing components for theperfluoroalkylalkylcarboxylic acid esters, containing hydroxyl groups,according to the invention.

As such crosslinking components there may especially be mentioned:epoxide compounds, namely polyglycidyl ethers, such as butanedioldiglycidyl ether and diglycidyl ether, diisocyanates andpolyisocyanates, such as 0-, mand p-phenylenediisocyanate,toluylene-2,4-diisocyanate and 1,S-naphthylenediisocyanate; acrylylcompounds such as methylene-bis-acrylamide and symmetricaltriacrylylperhydrotriazine; poly-(2,3-dihydro-l,4-pyranyl) compounds,such as (2,3-dihydro-1',4'-pyran-2'-yl)-methylester; aldehydes, such asformaldehyde or glyoxal, and soluble phenol-formaldehyde condensationproducts, such as novolaks or resols. Preferably, aminoplasts which aresoluble in water or in organic solvents are used as crosslinkingcomponents.

As such, there may be used formaldehyde condensation products of urea,thiourea, guanidine, acetylenediurea and dicyandiamide, and also ofaminotriazines, such as melamine, or of guanamines, such asacetoguanamine, benzoguanamine, tetrahydrobenzoguanan'iine orformoguanamine as well as their ethers with alcohols, such as methyl,ethyl, propyl, allyl, butyl, amyl and hexyl alcohol, cyclohexanol,benzyl alcohol, lauryl alcohol, and stearyl, oleyl or abietyl alcohol.In addition to the ether radicals, the condensation products can alsofurther contain radicals of higher-molecular acids, such as for examplestearic acids.

Particularly good technical results in the field of textile finishingare obtained on using water-soluble condensation products offormaldehyde and melamine and especially the esterification product oretherification product of hexamethylolmelamine-methyl-ether and stearicacid or stearyl alcohol as crosslinking components.

The perfluoroalkylalkylmonocarboxylic acid esters can also be used as amixture with polymers not containing fluorine. Very suitable polymersnot containing fluorine are here, for example, the homopolymers ofacrylic or methacrylic acid esters, such as poly(ethyl acrylate) orcopolymers of acrylic or methacrylic acid esters with methylolacrylamideor methylolmethacrylamide.

The perfluoroalkylalkylmonocarboxylic acid esters according to theinvention can, by virtue of their reactive groupings, be used for thetreatment of porous and nonporous substrates, preferably for producingoleophobic finishes thereon, and can be incorporated into the materialin question or above all applied to its surface. By porous substrates,there are to be understood leather or preferably fibre materials such astextiles and paper, whilst possible non-porous materials are plasticsand above all surfaces of metals and glass.

The finishing of the substrate with theperfluoroalkylalkylmonocarboxylic acid esters according to the inventioncan be carried out in a process stage by itself, but also in the sameprocess stage as the application of further finishing agents, forexample together with known agents for conferring hydrophobic propertiessuch as paraffin emulsions or solutions or emulsions of fatty acidcondensation products, for example with aminoplasts precondensates.

Further, a so-called soil release and anti-soiling effect can also beachieved with the perfiuoro compounds according to the invention,especially on cotton.

Simultaneously with the effect of imparting an oleophobic finish, theseperfluoro compounds also show hydrophilic properties. For imparting anoleophobic finish, the substrates can be treated either with solutionsor with dispersions or emulsions of the perfiuoro compounds.Perfluoroalkylalkylmonocarboxylic acid esters can for example also beapplied to the textile material as a solution in an organic solvent, andbe fixed thermally to the fabric after evaporation of the solvent.

Textile materials are of particular interest for finishing by means ofthe perfiuoroalkylalkylmonocarboxylic acid esters according to theinvention. Textile materials for example include those of native orregenerated cellulose, such as cotton, linen or rayon, viscose staple orcellulose acetate. However, textiles of wool, synthetic polyamides,polyesters or polyacrylonitrile can also be treated. Mixed woven fabricsor mixed knitted fabrics of cottonpolyester fibres can also be finishedadvantageously. The textiles can in these cases be in the form offilaments, fibres or flocks, but preferably of woven fabrics or knittedfabrics.

Preparations which contain the perfiuoro compounds according to theinvention can be applied to the substrate in a customary manner which isin itself known. Woven fabrics can for example be impregnated by theexhaustion process or on a padder which is charged with the preparationat room temperature. The impregnated material is thereafter dried at 60to 120 C. and is subsequently optionally further subjected to a heattreatment at over 100 C., for example at 120 to 200 C.

The textiles thus treated as a rule show an oil-repellent effect andwhere the preparation additionally contains an agent for conferringhydrophobic properties, this effect is coupled with a water-repellenteffect.

EXAMPLE '1 4.6 g. of epichlorohydrin and 22.1 g. of2,2,3,3-H-pentadecafluorodecylic acid are dissolved at room temperaturein 100 ml. of ethyl acetate, with the addition of 1 g. of anhydroussodium acetate.

The temperature rises to 25. C. The reaction temperature is keptconstant at 50 C. and after 18 hours reaction the epoxide content is Thesolution is concentrated in vacuo at 40 'C. The residue is taken up in100 ml. of diethyl ether and washed 3 times with 20 ml. of water, andyields a light yellow phase. Weight 17.3 g.'=70.04% of theory.

The structure is confirmed by recording a mass spectrum in that thisshows a molecular weight of 534-536, which corresponds to a product ofthe formula (VIII).

6 EXAMPLE 2 9.25 g. of epichlorohydrin and 49.2 g. ofperfluoroalkylalkylmonocarboxylic acid together with 2 g. of sodiumacetate (anhydrous), are dissolved in 100 ml. of ethyl acetate.

The reaction mixture is kept for 7 hours at C. After completion of thereaction, the solution is freed of the sodium acetate by filtration andthe solvent is removed in vacuo.

A water-soluble substance is thereby isolated. Yield 45 g.=73.4% oftheory.

The structure is confirmed by recording a mass spectrum, in thatmolecular weights of 684, 612, 712 and 640 are found, which correspondsto a formula HO- a EXAMPLE 3 7.4 g. of glycidol together with 49.2 g. ofperfluoroalkylalkylmonocarboxylic acid and 2 g. of sodium acetate(anhydrous) are dissolved in ml. of ethyl acetate.

The reaction mixture is kept for 9 hours at 80 C. After completion ofthe reaction, the solution is freed of the sodium acetate by filtration,and the solvent is removed in vacuo. A water-soluble substance isthereby isolated. Yield: 51.5 g.=89.5%.

The structure is confirmed by recording a mass spectrum, in thatmolecular weights of 666, 622, 594 and 694 are found, which correspondsto a product of the formula (IX).

EXAMPLE 4 7.4 g. glycidol together with 60.4 g. ofperfiuoroalkyldecylcarboxylic acid 3 and 2 g. of anhydrous sodiumacetate are dissolved in 400 ml. of ethyl acetate, and thereafter thereaction is carried out as described in Example 2 and 3.

Yield: 47.2 g.=69.62% of theory.

The substance is waxy. The structure is confirmed by recording a massspectrum, in that this shows molecular weights of 578, 678 and 778,which corresponds to the following structure:

(2) [CF (CF2)v(CH2)10'-COO CHCH2OH EXAMPLE 5 7.4 g. of glycidol togetherwith 54.6 g. of perfluoroalkylcyclohexylcarboxylic acid and 2 g. ofanhydrous Na acetate are dissolved in 400 ml. of ethyl acetate and thereaction is carried out as described in Example 2 and 3.

Yield: 32.5 g.=52.4% of theory.

The substance is viscous and light yellow. The structure is confirmed byrecording a mass spectrum, in that this Theperfiuoroalkylalkylmonocarboxylic acid used has the shows molecularweights of 520, 620 and 720, which corresponds to the followingstructure:

Fs( 2)v COO 43 H-CH: O H

a(C zla -CO OH C a( all;

Co OH EXAMPLE 6 32 g. of perfluoroalkylalkylmonocarboxylic acid togetherwith 21.1 g. of polyethylene glycol-diglycid (average molecular weightof the polyethylene glyco1=300) and 1 g. of anhydrous sodium acetate aredissolved in 150 ml. of ethyl acetate. I

The reaction is carried out as described in Example 2 and 3 and yields51.3 g.=96.6% of theory of a light brown wax of the presumed formula:

v=7, 9, 11; w=2, 4, 6; x= to 10.

dissolved in 30 ml. of ethyl acetate and 0.5 g. of sodium acetate(anhydrous) is added. 2.12 g. of ethylene diglycid dissolved in 10 ml.of ethyl acetate are added dropwise.

The reaction and working up take place as indicated in Examples 2 and 3.

Yield: 7.3 g.=89.7% of theory.

The structure is confirmed after recording a mass spectrum.

2 g. of the end product according to Example 1 are dissolved in 10 ml.of ethyl acetate. Woven pieces of wool are dipped into the solution, andthus impregnated. A

piece of filter paper is impregnated in the same manner.

The fabric sample and paper sample are thereafter dried for 10 minutesat 130 C. in vacuo.

The assessernent of the oil-repellent effect is carried out according tothe so-called 3M oil repellency test (Crajech and Petersen, TextileResearch Journal 32, pages 320 to 331 1960) using heptane-Nujolmixtures. In the assessment, 150 denotes the best achievable rating.Individual samples are assessed immediately after drying.

The wool fabric sample is given a rating of 70 and the paper sample arating of 90. The finish is of oleophobic character.

EXAMPLE 9 The following liquors are prepared from the products ofExamples 2 to 7 (concentrations in g./l.)

Constituents Liquor A B C D E F Product from- Example 2.

Example 3 Example 4.

Example 5 Example 6..

Example 7. Dimethylolglyoxal monourein Dioxane 50% strength aqueoussolution of 1 mol of hexamethylolmelamlne-hexamethyl-ether and 1 mol ofdlmethylol urea *Hexamethylolmelamine-pentamethyl-ether EXAMPLE 7 6 g.of perfluoroalkylalkylmonocarboxylic acid are I Theperfluoroalkylalkylmonocarboxylic acid used has the followingcomposition:

Pieces of woven fabric of cotton and, in part, cottonpolyester aresuccessively dipped into this liquor, thereby impregnated with theperfiuoro compound, and thereafter dried at C. for 5 minutes in vacuo,in the course of which the resin finish cures.

The assessment of the oil-repellent effect is made as indicated inExample 8, but in part also after 1, 5 and 10 SNV-3-washes (SNV-3-wash:wash for 30 minutes at 60 C. in a washing liquor which per litrecontains 5 g. of soap and 2 g. of anhydrous sodium carbonate, using aliquor ratio of 1:50).

The results are summarisedin the table below: group, with Y;representing a hydrogen atom, an alkyl Liquor Substrate A B C D E F G HI J K 110 120 120 110 110 90 90 120 100 100 100 110 110 100 so so 5o 50100 110 C ioi sr vva 100 110 on no yes er as sue 100 120 11 IXSNVB. 1000 28 x SNV3 90 100 90 xSNV3 so 100 so Cotton-polyester fabrics whichhave been finished with the liquors A, B, C, H and I, are additionallyalso tested for the soil-release effectiveness of the finishes. In this,the test specimens are spotted with synthetic, skin grease (Spangler,Cross and Sohaafsma, J. Am. Oil Soc. 43, 723, 1965) and Nujol.

The spots are applied before the first, and in part also before thefifth and tenth, SNV-3 wash, and subsequently assessed. The samples aregraded according to ratings 1 to 5, with rating 5 denoting completelywashed out and rating 1 not washed out, that is to say 5 is the bestrating.

1. Perfluoroalkylalkylmonocarboxylic acid esters corresponding to theformula R-Q-COO-A-X wherein R denotes a perfluoroalkyl radical with 4 to14 carbon atoms, Q denotes an acyclic alkyl radical with 1 to 10 carbonatoms, or a cycloalkylene radical with 5 or 6 ring carbon atoms, Adenotes an alkylene radical with 2 to 18 carbon atoms and X denotes ahalogen atom, a hydroxyl group or a Y--O(CH CH O),, group, each of saidX substituents being attached to a carbon atom other than the onecarrying the hydroxyl group 1), wherein Y represents a hydrogen atom, analkyl radical with 1 to 4 carbon atoms or an epoxyalkyl radical with 2to 4 carbon atoms, n is an integer having a value of 1 to 20, and thehydroxyl group (1) is in the 2-position to the R-QCOO group.

2. Perfluoroalkylalkylmonocarboxylic acid esters according to claim 1,characterised in that they correspond to the formula H (1 wherein R, Aand X have the meaning indicated in claim 2, p denotes an integer havinga value of 1 to 10, and the hydroxyl group (1) is in the 2-position tothe 3. Perfiuoroalkylalkylmonocarboxylic acid esters according to claim2, characterised in that p is an integer having a value of 2 to 6.

4. Perfluoroalkylalkylmonocarboxylic acid esters according to claim 1characterised in that they correspond to the formula [R' (CH2)|11C o O]-CHA5 I: [110-] -13H-A4-X2 wherein R has the meaning indicated in claim2 and p is 1 to 10, A denotes a hydrogen atom or an alkyl radical with 1to 8 carbon atoms, A, denotes an alkylene radical with 1 to 8 carbonatoms and X denotes a chlorine atom or bromine atom, a hydroxy group ora group with 1 to 4 carbon atoms or an epoxyalkyl group with 2 to 4carbon atoms, and n is an integer having a value of 1 to 20.

5. Perfiuoroalkylalkylmonocarboxylic acid esters according to claim 1characterised in that they correspond to the formula wherein R has themeaning indicated in claim 2 and A is an alkylene radical with 1 to 8carbon atoms, p is an integer having a value of 2 to 6, A denotes ahydrogen atom or a methyl or ethyl group, and X denotes a ch10- rine orbromine atom or a hydroxyl or group, wherein Y represents a hydrogenatom or a methyl or glycidyl group and n is an integer from 1 to 15.

6. Perfluoroalkylalkylmonocarboxylic acid esters according to claim 1characterised in that they correspond to the formula wherein X denoteschlorine or hydroxyl and R has the meaning indicated in claim 2, and pis 2 to 6.

7. Perfiuoroalkylalkylmonocarboxylic acid esters according to claim 1characterised in that they contain a perfluoroalkyl radical with 5 to 11carbon atoms.

8. Perfiuoroalkylalkylmonocarboxylic acid esters according to claim 1,characterised in that they contain a perfluoroalkyl radical with 7 to 9carbon atoms.

9. Perfluoroalkylalkylmonocarboxylic acid esters of the formula 10.Prefiuoroalkylalkylmonocarboxylic acid esters of the formula[mo-(0F.).(0H,),.-co0-1 CH:

no-1 JJHCH:OH]]

wherein v denotes 5, 7 or 9 and w denotes 2, 4 or 6.

References Cited UNITED STATES PATENTS ELBERT L. ROBERTS, PrimaryExaminer D. G. RIVERS, Assistant Examiner US. Cl. X.R.

117-121, 124, 127, 138.8 F, 138.8 M, 138.8 UA, 141, 143, 144, 154;260-348 A, 404.5 468 I, 486 H, 487

